WO2014057992A1 - 多価置換ビフェニル化合物の製造方法及びそれに用いられる固体触媒 - Google Patents
多価置換ビフェニル化合物の製造方法及びそれに用いられる固体触媒 Download PDFInfo
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Definitions
- the present invention relates to a method for producing a polyvalent substituted biphenyl compound and a solid catalyst used therefor.
- An object of the present invention is to provide a method for producing a polyvalent substituted biphenyl compound and a solid catalyst used therefor, which can obtain the polyvalent substituted biphenyl compound in a high yield without going through complicated steps. To do.
- the present invention is represented by the following general formula (2), comprising a step of coupling a substituted benzene compound represented by the following general formula (1) in the presence of a solid catalyst in which gold is immobilized on a support.
- a method for producing a polyvalent substituted biphenyl compound is provided.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- n is an integer of 1 to 3.
- n is any integer of 1 to 3 and two Rs bonded to adjacent carbon atoms are both carboxyl groups
- the carboxyl groups may be bonded to each other to form an anhydride.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- Plural n and R may be the same or different.
- the carboxyl groups are bonded to each other to form an anhydride. May be formed.
- a polyvalent substituted biphenyl compound can be obtained in a high yield without going through complicated steps.
- the substituted benzene compound represented by the general formula (1) is a substituted benzene compound represented by the following general formula (1) ′
- the polyvalent substituted biphenyl compound represented by the general formula (2) is represented by the following general formula: (2) It is preferable that it is a compound represented by '.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- m represents 0 or 1.
- m represents 1
- two Rs are the same.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- m represents 0 or 1.
- a plurality of m and R may be the same or different.
- R in the general formulas (1) and (2) or the general formulas (1) ′ and (2) ′ is preferably an alkyl group, a carboxyl group or an alkoxycarbonyl group, and an alkyl group or an alkoxycarbonyl group. It is more preferable that
- M in the general formulas (1) ′ and (2) ′ is 1, and an s-form represented by the following general formula (2s) in the polysubstituted biphenyl compound represented by the general formula (2) ′ And the a-form represented by the following general formula (2a) (s / a ratio) is preferably 2.0 or more.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or a carboxyl group which may be esterified.
- a plurality of R may be the same or different and are bonded to adjacent carbon atoms. When both R are the above carboxyl groups, the carboxyl groups may be bonded to each other to form an anhydride.
- the substituted benzene compound represented by the general formula (1) is preferably further coupled in the presence of a solvent, the solvent is more preferably an organic carboxylic acid, and the organic carboxylic acid is acetic acid. More preferably.
- a polyvalent substituted biphenyl compound can be obtained with a higher yield.
- a compound having m of 1 in the general formula (1) ′ is used as a substrate, a polyvalent substituted biphenyl compound can be obtained with a high s / a ratio.
- the substituted benzene compound represented by the general formula (1) is preferably coupled in a gas containing oxygen.
- a polyvalent substituted biphenyl compound can be obtained with a higher yield.
- the present invention also provides a solid catalyst for producing a polyvalent substituted biphenyl compound represented by the following general formula (2), comprising a support and gold immobilized on the support.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- Plural n and R may be the same or different. In the case where n is any integer of 1 to 3 and two Rs bonded to adjacent carbon atoms are both the above carboxyl groups, the carboxyl groups are bonded to each other to form an anhydride. May be formed.
- the polyvalent substituted biphenyl compound can be obtained in a high yield without going through a complicated process.
- the present invention also provides use of a solid catalyst comprising a support and gold immobilized on the support for the production of a polyvalent substituted biphenyl compound represented by the following general formula (2).
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- Plural n and R may be the same or different. In the case where n is any integer of 1 to 3 and two Rs bonded to adjacent carbon atoms are both the above carboxyl groups, the carboxyl groups are bonded to each other to form an anhydride. May be formed.
- the carrier is preferably a metal oxide.
- the catalyst life tends to be long or the reaction rate tends to be high.
- the metal oxide is cobalt (Co), manganese (Mn), iron (Fe), cerium (Ce), zirconium (Zr), nickel (Ni), titanium (Ti), lanthanum (La), silicon ( It is preferably an oxide of at least one metal selected from the group consisting of Si) and aluminum (Al), and at least one metal selected from the group consisting of manganese (Mn), cobalt (Co) and zirconium (Zr) It is more preferable that the oxide is.
- a polyvalent substituted biphenyl compound can be obtained with a higher yield.
- gold particles having an average particle diameter of 0.5 to 10 nm are immobilized on the carrier.
- the average particle diameter of the gold particles is in the above range, the yield and reaction rate of the coupling reaction are further improved.
- a compound having m of 1 in the general formula (1) ' is used as a substrate, a substituted biphenyl compound can be obtained with a high s / a ratio.
- the present invention it is possible to provide a method for producing a polyvalent substituted biphenyl compound and a solid catalyst used therefor, which can obtain the polyvalent substituted biphenyl compound in a high yield without going through complicated steps. it can.
- the solid catalyst obtained in the present invention can be recovered and reused after the reaction.
- FIG. 1 is a gas chromatography chart of the reaction solution obtained in Example 2-38.
- FIG. 2 is a high performance liquid chromatography (HPLC) chart of the reaction solution obtained in Example 2-39.
- FIG. 3 is an X-ray diffraction pattern of manganese dioxide obtained in Reference Example 1-21.
- the method for producing a polyvalent substituted biphenyl compound of the present embodiment includes a step of coupling substituted benzene compounds with each other in the presence of a solid catalyst.
- the solid catalyst of this embodiment is one in which gold is physically or chemically immobilized (sometimes referred to as “supported”) on a support.
- the primary particle diameter of the solid catalyst described below represents the particle diameter of each particle (primary particle) forming the solid catalyst.
- the particle size of the gold particles represents the particle size of each gold particle immobilized on the solid catalyst.
- the shape of the solid catalyst may be appropriately selected according to the mode of use, and is preferably in the form of particles.
- the form of the solid catalyst may be any form such as a dense body and a porous body.
- the average primary particle size of the solid catalyst is preferably 5 nm to 1 mm, more preferably 5 nm to 10 ⁇ m, and further preferably 5 nm to 100 nm.
- the average primary particle size referred to here is, for example, by creating a particle size distribution with a scanning electron microscope (SEM) observation, a transmission electron microscope (TEM) observation, or a laser diffraction scattering type particle size distribution measuring device. It is the average value of the number-based particle size obtained.
- the gold is preferably immobilized on the carrier in the form of a film or particles, and more preferably in the form of particles.
- the immobilized gold particles When gold is immobilized on the carrier in the form of particles, it is desirable that the immobilized gold particles have the same particle diameter.
- the average particle diameter of the gold particles is preferably 20 nm or less, more preferably 10 nm or less, further preferably 5 nm or less, and preferably 0.5 nm or more.
- the coupling reaction efficiency per unit mass of the immobilized gold that is, the catalyst rotation speed per unit time can be increased.
- the gold is uniformly dispersed and immobilized on the surface of the carrier.
- the dispersion state is controlled by the amount of gold immobilized on the carrier, the selection of the carrier, the method of immobilizing gold on the carrier, and the like.
- the amount of gold immobilized on the carrier may depend on the state and size of the gold (particle diameter in the case of particles).
- the amount of gold immobilized on the support is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the entire solid catalyst.
- the amount of gold immobilized is not less than the lower limit of the above range, a desired reaction rate tends to be obtained even with a small amount of solid catalyst, and when the amount of gold immobilized is not more than the upper limit of the above range,
- the coupling reaction efficiency per unit mass of the catalyst that is, the number of catalyst rotations per unit time can be improved, which tends to be economically advantageous.
- the average particle size of the gold particles immobilized on the carrier can be evaluated by creating a particle size distribution of the gold particles by observation with a transmission electron microscope (TEM).
- the amount of metal (for example, the amount of immobilized gold) of the solid catalyst can be measured by, for example, inductively coupled plasma emission spectroscopy (ICP-AES).
- ICP-AES inductively coupled plasma emission spectroscopy
- the type of atoms present in the solid catalyst and the state of gold dispersion should be confirmed using a transmission electron microscope (TEM), an X-ray photoelectron spectrometer (ESCA), and X-ray diffraction (XRD). Can do.
- the carrier is not particularly limited as long as it is generally used as a carrier for a solid catalyst, and any of inorganic compounds and organic compounds can be employed.
- the carrier include nickel oxide, zinc oxide, iron oxide, cobalt oxide, manganese dioxide, copper oxide, silicon oxide, tin oxide, aluminum oxide, barium oxide, titanium oxide, vanadium oxide, tungsten oxide, molybdenum oxide, niobium oxide.
- Metal oxides such as tantalum oxide, cerium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, magnesium oxide, beryllium oxide, chromium oxide, scandium oxide, cadmium oxide, and indium oxide, or composite oxides combining these metal oxides Carbon black; organic polymer; zeolite; mesoporous silicate; clay; diatomaceous earth; and pumice.
- the support is preferably made of an inorganic compound, more preferably a metal oxide, for reasons such as easy manufacture and use at high temperatures. When the support is a metal oxide, the catalyst life tends to be long or the reaction rate tends to be high.
- carriers may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the metal oxides are cobalt (Co), manganese (Mn), iron (Fe), cerium (Ce), zirconium (Zr), nickel (Ni), titanium (Ti), lanthanum (La), silicon (Si). And an oxide of at least one metal selected from the group consisting of aluminum (Al) and oxidation of at least one metal selected from the group consisting of manganese (Mn), cobalt (Co) and zirconium (Zr) More preferably, it is a product.
- a polyvalent substituted biphenyl compound tends to be obtained with a higher yield.
- a substituted biphenyl compound can be obtained with a high s / a ratio when a compound having m of 1 in the general formula (1) ′ is used as a substrate.
- the shape of the carrier used for the production of the solid catalyst may be appropriately selected according to the mode of use, and is preferably in the form of particles.
- the form of the carrier may be any form such as a dense body and a porous body.
- the size of the carrier (average primary particle size in the case of particles) is preferably 5 nm to 1 mm, more preferably 5 nm to 10 ⁇ m, and further preferably 5 nm to 100 nm.
- the size of the carrier can be measured as a number-based particle size by, for example, scanning electron microscope (SEM) observation, transmission electron microscope (TEM) observation, or a laser diffraction / scattering particle size distribution analyzer.
- the production method of the solid catalyst is not particularly limited, and examples thereof include a coprecipitation method, a precipitation precipitation method, an impregnation method, an evaporation to dryness method, a pore filling method, and an ion exchange method.
- a coprecipitation method since it is possible to immobilize gold on many types of carriers and to control the particle size of gold immobilized on the carriers to be small, the coprecipitation method described below Alternatively, the precipitation method is preferable.
- gold tends to be uniformly dispersed and immobilized on the surface of the support.
- the solid catalyst on which gold is immobilized may be calcined in an air atmosphere, a hydrogen atmosphere, or an inert gas atmosphere.
- a gold compound aqueous solution whose pH is adjusted to a range of 7 to 10 by adding a basic compound, an oxide powder as a carrier, or the above powder is supported on a support such as a spherical shape, a cylindrical shape or a honeycomb shape.
- the formed molded body is suspended or immersed, and gold hydroxide is deposited and precipitated on the surface of the oxide carrier.
- the carrier on which the gold hydroxide is deposited and washed is washed with water, dried, and calcined in an arbitrary atmosphere, whereby a solid catalyst having gold immobilized thereon can be obtained.
- the aforementioned basic compound is appropriately selected according to the solid catalyst to be prepared, and for example, sodium hydroxide and urea are used.
- the substituted benzene compound used as a substrate in the coupling reaction of this embodiment is a compound represented by the following general formula (1).
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- n is an integer of 1 to 3.
- the carboxyl groups may be bonded to each other to form an anhydride.
- the substituted benzene compound is preferably a compound represented by the following general formula (1) ′.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- m represents 0 or 1.
- m represents 1
- two Rs are the same.
- m is 1 and two Rs are both the above carboxyl groups, the carboxyl groups may be bonded to each other to form an anhydride.
- the alkyl group of R in the general formulas (1) and (1) ′ is preferably an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom of the alkyl group may be substituted with a halogen atom.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a trifluoromethyl group, and a methyl group or an ethyl group is preferable.
- the R alkoxy group in the general formulas (1) and (1) ′ is preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentyloxy group. Etc., and preferably a methoxy group or an ethoxy group.
- the R carboxyl group which may be esterified is preferably a carboxyl group or an alkyl ester (alkoxycarbonyl group) of the carboxyl group.
- the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Group or ethyl group.
- substituted benzene compound represented by the general formula (1) ′ include toluene, ethylbenzene, butylbenzene, o-xylene, o-dimethoxybenzene, methyl benzoate, butyl benzoate, dimethyl phthalate, and phthalic acid. Examples include diethyl and phthalic anhydride.
- Specific examples of the substituted benzene compound represented by the general formula (1) other than the substituted benzene compound represented by the general formula (1) ′ include trifluoromethylbenzene, p-dimethoxybenzene, and 2,3. , 6-trimethylphenol and the like.
- the substituted benzene compounds may be coupled in the presence of a solvent.
- the solvent is not particularly limited as long as it does not inhibit the coupling reaction.
- the solvent is not particularly limited as long as it does not inhibit the coupling reaction.
- water acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, etc.
- ethers such as diethyl ether, tetrahydrofuran, and dioxane
- Organic ester compounds, and ketone compounds such as n-butyl methyl ketone, methyl ethyl ketone, and isopropyl ethyl ketone.
- an organic carboxylic acid more preferably acetic acid, is used.
- 1 type of these solvents may be used independently, and 2 or more types may be mixed and used for them.
- a solvent preferably an organic carboxylic acid, more preferably acetic acid
- a solvent preferably an organic carboxylic acid, more preferably acetic acid
- a polyvalent substituted biphenyl compound can be obtained with a high s / a ratio.
- the substituted benzene compounds may be coupled with each other in the presence of only the solid catalyst without using a solvent.
- the coupling reaction of the substituted benzene compound of the present embodiment is performed by a method such as mixing the above-mentioned solid catalyst and the above-described substituted benzene compound with a solvent as necessary and reacting them with stirring.
- the temperature of the coupling reaction is preferably 50 to 250 ° C., more preferably 100 to 200 ° C.
- the reaction pressure is preferably 0.1 to 5 MPa, more preferably 0.1 to 2.5 MPa.
- the reaction form may be any form of batch or distribution, gas phase or liquid phase, fixed bed or fluidized bed.
- the reaction atmosphere in the coupling reaction of this embodiment is not particularly limited, and examples thereof include inert gases such as nitrogen, helium, and argon; and oxidizing gases such as oxygen and ozone.
- the coupling reaction is preferably performed in an oxidizing gas, more preferably in a gas containing oxygen.
- the inert gas is preferably nitrogen.
- nitrogen, oxygen, and a mixture of nitrogen and oxygen eg, air
- another gas that does not participate in the reaction such as carbon dioxide, may be included.
- the amount of the solid catalyst used in the coupling reaction is determined by the ratio between the total number of moles of the substituted benzene compound and the total number of moles of gold immobilized on the support.
- the gold immobilized on the carrier is preferably from 0.01 mol% to 100 mol%, more preferably from 0.03 mol% to 80 mol%, more preferably from 0.05 mol% to the total number of moles of the substituted benzene compound. % To 50 mol% is more preferable, and 0.1 mol% to 10 mol% is particularly preferable.
- the ratio of the number of moles of gold immobilized on the support to the total number of moles of the substituted benzene compound is simply expressed as the number of equivalents (mol%) of the solid catalyst. And so on.
- the amount used when a solvent is used is preferably 0 to 10 mL, more preferably 0 to 2.5 mL, with respect to 1 g of the substituted benzene compound.
- the polyvalent substituted biphenyl compound obtained by the coupling reaction of this embodiment is isolated and purified by a general method such as filtration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. it can.
- the polyvalent substituted biphenyl compound obtained by the production method of the present embodiment has a structure represented by the following general formula (2).
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- n represents an integer of 0 to 3.
- n is an integer of 1 to 3.
- the carboxyl groups may be bonded to each other to form an anhydride.
- the polyvalent substituted biphenyl compound is preferably a compound represented by the following general formula (2) ′ obtained by coupling substituted benzene compounds represented by the general formula (1) ′.
- R represents an alkyl group, an alkoxy group, a hydroxy group, or an optionally esterified carboxyl group
- m represents 0 or 1.
- a plurality of m and R may be the same or different.
- m is 1 and two Rs bonded to adjacent carbon atoms are both carboxyl groups, the carboxyl groups may be bonded to each other to form an anhydride.
- the alkyl group, alkoxy group, and optionally esterified carboxyl group of R are as defined in the general formulas (1) and (1) ′.
- the substituted benzene compound is a compound in which n in the general formula (1) is 0, the resulting polysubstituted biphenyl compound is a disubstituted biphenyl compound, and when n is a compound of 1, a tetrasubstituted biphenyl is obtained. When it is a compound and n is a compound of 3, it becomes an octasubstituted biphenyl compound.
- a substituted benzene compound is coupled by the production method of this embodiment, a symmetrically substituted biphenyl (meaning a biphenyl having a substituent at a symmetrical position on two benzene rings) and an asymmetrically substituted biphenyl (two An isomer consisting of biphenyls having a substituent at an asymmetric position on the benzene ring is obtained.
- the substituted benzene compound is a compound in which m in the general formula (1) ′ is 1
- the symmetric substituted biphenyls represented by the following general formula (2s) hereinafter referred to as “s-form”
- tetrasubstituted biphenyl compounds of asymmetrically substituted biphenyls represented by the general formula (2a) hereinafter sometimes referred to as “a-isomer” are produced as the main isomers.
- R is the carboxyl group
- the carboxyl groups may be bonded to each other to form an anhydride represented by the following formula (3).
- the yield of the polyvalent substituted biphenyl compound obtained as described above is, for example, preferably 1% or more, more preferably 3% or more, further preferably 5% or more, 10%
- the above is particularly preferable.
- the s / a ratio described later is, for example, preferably 2.0 or more, more preferably 3.0 or more, further preferably 5.0 or more, and 10.0 or more. Is more preferable, and 20.0 or more is particularly preferable.
- the method for producing a polyvalent substituted biphenyl compound of this embodiment may further include a step of oxidizing the alkyl group.
- R can be converted into a carboxyl group by the oxidation step.
- the method for producing a polyvalent substituted biphenyl compound of the present embodiment hydrolyzes the esterified carboxyl group. You may further provide the process.
- R can be converted into a carboxyl group by the hydrolysis step.
- the manufacturing method of the polyvalent substituted biphenyl compound of this embodiment dehydrates the said carboxyl group.
- the process to perform may be further provided.
- the two Rs bonded to adjacent carbon atoms can be bonded to each other to form an anhydride.
- 3,3 ′, 4,4′-tetraalkylbiphenyl by oxidizing the alkyl group, 3,3 ′, 4,4′-biphenyltetracarboxylic acid and / or 3,3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride.
- 3,3 ′, 4,4′-biphenyltetracarboxylic acid can be derived into 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride by further dehydration.
- the oxidation step can be performed, for example, by a method described in International Publication No. 2012/046857, International Publication No. 2012/155749, or the like.
- it is preferably represented by the general formula (1) in the presence of a metal compound containing at least one metal selected from the group consisting of cobalt, manganese and zirconium, and an imide compound such as N-hydroxyphthalimide. It is preferable to oxidize a polyvalent substituted biphenyl compound in which R of the compound is an alkyl group with molecular oxygen.
- hydrolysis and dehydration can be performed by methods described in, for example, Japanese Patent No. 4048689 and Japanese Patent No. 4977789.
- the hydrolysis is preferably performed by adding pure water only and heating under pressure.
- Dehydration is preferably performed by heating and stirring at 180 to 195 ° C. in an inert gas atmosphere.
- the obtained polyvalent substituted biphenyl compound may have multiple types of isomers.
- what is necessary is just to isolate
- 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is a useful compound as a raw material for polyimide.
- the primary particles of the support and the solid catalyst and the gold particles on the support are observed by TEM, and the diameters of the circles circumscribed by the particles in the TEM photograph (the circumscribed circle) are measured.
- the particle diameter and the particle diameter of the gold particles on the carrier were used.
- the number average diameter of the support, the solid catalyst, and the gold particles on the support was calculated by measuring the particle size of 10 or more arbitrarily selected particles and creating a particle size distribution. The calculated number average diameter was defined as the average primary particle diameter of the support and the solid catalyst and the average particle diameter of the gold particles, respectively.
- the gold particles on the carrier were specified by energy dispersive X-ray spectroscopy (EDS) measurement.
- EDS energy dispersive X-ray spectroscopy
- the solid catalyst was dissolved by warming with aqua regia and diluted with ultrapure water.
- the emission intensity of gold dissolved in the liquid was measured by induction plasma emission spectroscopy (ICP-AES).
- the amount of gold dissolved in the liquid was calculated by comparing the light emission intensity of gold dissolved in the liquid with the light emission intensity of gold in a standard solution having a known gold concentration. From the dissolution amount, the gold content contained in the unit mass of the solid catalyst, that is, the gold immobilization amount (% by mass) was calculated.
- the products are 3,3 ′, 4,4′-tetramethylbiphenyl (s-form) and 2,3,3 ′, 4′-tetramethylbiphenyl (a- Body).
- Example 1-1 Synthesis of a solid catalyst in which gold is immobilized on cobalt oxide (hereinafter also referred to as “Au / Co 3 O 4 ”)) Cobalt nitrate (II) hexahydrate 5.52 g and tetrachloroauric acid tetrahydrate 0.41 g were dissolved in distilled water 200 mL at room temperature (aqueous solution 1). Separately, 2.63 g of sodium carbonate was dissolved in 200 mL of distilled water (aqueous solution 2). Next, the aqueous solution 1 was added to the aqueous solution 2 at once, and the mixture was stirred at room temperature for 3 hours.
- Cobalt nitrate (II) hexahydrate 5.52 g and tetrachloroauric acid tetrahydrate 0.41 g were dissolved in distilled water 200 mL at room temperature (aqueous solution 1). Separately, 2.63 g of sodium carbonate was dissolved in 200 mL of
- the produced precipitate was washed with distilled water and filtered until the pH became constant.
- the filtrate was dried at 70 ° C. overnight.
- calcination was performed in air at 300 ° C. for 4 hours to obtain a solid catalyst (Au / Co 3 O 4 ) in which gold was immobilized on cobalt oxide.
- the average primary particle size of the obtained solid catalyst was about 15 nm, the amount of gold immobilized was 10% by mass, and the average particle size of the gold particles on the support was 2 nm.
- Example 1-2 (Synthesis of solid catalyst in which gold is immobilized on nickel oxide (hereinafter also referred to as “Au / NiO”)) Nickel nitrate hexahydrate 5.53 g and tetrachloroauric acid tetrahydrate 0.41 g were dissolved in distilled water 200 mL at room temperature and heated to 70 ° C. (aqueous solution 3). Separately, 2.67 g of sodium carbonate was dissolved in 250 mL of distilled water and heated to 70 ° C. (aqueous solution 4). Next, the aqueous solution 3 was added to the aqueous solution 4 all at once, and the mixture was stirred at 70 ° C. for 1 hour.
- Au / NiO nickel oxide
- the produced precipitate was washed with distilled water and filtered until the pH became constant.
- the filtrate was dried at 70 ° C. overnight.
- calcination was performed in air at 300 ° C. for 4 hours to obtain a solid catalyst (Au / NiO) in which gold was immobilized on nickel oxide.
- the average primary particle size of the obtained solid catalyst was about 5 nm, the gold immobilization amount was 10% by mass, and the average particle size of the gold particles on the support was 4 nm.
- Example 1-3 Synthesis of a solid catalyst in which gold is immobilized on iron oxide (hereinafter also referred to as “Au / Fe 2 O 3 ”)) 7.68 g of iron (II) nitrate nonahydrate and 0.41 g of tetrachloroauric acid tetrahydrate were dissolved in 200 mL of distilled water at room temperature (aqueous solution 5). On the other hand, 3.88 g of sodium carbonate was dissolved in 370 mL of distilled water and heated to 70 ° C. (aqueous solution 6). Next, the aqueous solution 5 was added to the aqueous solution 6 all at once, and the mixed solution was stirred at 70 ° C. for 1 hour.
- the produced precipitate was washed with distilled water and filtered until the pH became constant. The filtrate was dried at 80 ° C. overnight. After drying, the solid catalyst (Au / Fe 2 O 3 ) in which gold was immobilized on iron oxide was obtained by baking in air at 300 ° C. for 4 hours.
- the average primary particle size of the obtained solid catalyst was about 20 nm, the gold immobilization amount was 9% by mass, and the average particle size of the gold particles on the support was 4 nm.
- Example 1-4 Synthesis of a solid catalyst in which gold is immobilized on cerium oxide (hereinafter also referred to as “Au / CeO 2 ”)
- Tetrachloroauric acid tetrahydrate 64 mg was dissolved in distilled water (155 mL), and the solution was adjusted to pH 7 by dropwise addition of an aqueous sodium hydroxide solution while heating to 70 ° C.
- Example 1-5 Synthesis of solid catalyst in which gold is immobilized on titanium oxide (hereinafter also referred to as “Au / TiO 2 ”) 22 mg of tetrachloroauric acid / tetrahydrate was dissolved in 52 mL of distilled water, and while heating to 70 ° C., an aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7. To this was added 1 g of titanium oxide (manufactured by Nippon Aerosil Co., Ltd., P-25 (trade name), average primary particle size 25 nm), and then stirred at 70 ° C. After 1 hour, the precipitate was washed with distilled water and filtered until the pH became constant.
- the filtrate was dried at 100 ° C. overnight. After drying, calcination was performed in air at 300 ° C. for 4 hours to obtain a solid catalyst (Au / TiO 2 ) in which gold was immobilized on titanium oxide.
- the average primary particle size of the obtained solid catalyst was about 25 nm, the gold immobilization amount was 0.8% by mass, and the average particle size of the gold particles on the support was 3 nm.
- Example 1-6 Synthesis of a solid catalyst in which gold and cobalt are immobilized on silica (hereinafter also referred to as “Au / Co / SiO 2 ”)
- 0.50 g of cobalt nitrate (II) hexahydrate was dissolved in 10 mL of distilled water, and silica (manufactured by Fuji Silysia Chemical Co., Ltd., CARiACT Q-15 (trade name), average primary particle size 75-150 ⁇ m).
- 85 g was added, and then 0.11 g of tetrachloroauric acid tetrahydrate was added. While stirring at room temperature, aqueous ammonia was added dropwise to adjust the pH of the solution to 8.5.
- the precipitate was washed with distilled water and filtered. The filtrate was dried at 120 ° C. for 20 hours. After drying, the solid catalyst (Au / Co / SiO 2 ) in which gold and cobalt were immobilized on silica was obtained by baking in air at 400 ° C. for 5 hours. The average primary particle size of the obtained solid catalyst was about 100 ⁇ m, and the amount of gold immobilized was 4 mass%.
- Example 1-7 Synthesis of cobalt oxide-solid catalyst in which gold is immobilized on cerium oxide (hereinafter also referred to as “Au / Co 3 O 4 —CeO 2 ”)) 21 mg of tetrachloroauric acid tetrahydrate was dissolved in 51 mL of distilled water, and an aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7.6. To this was added 1 g of cobalt oxide-cerium oxide (a composite oxide of cobalt oxide and cerium oxide, average primary particle size 40 nm), and the mixture was stirred at 70 ° C. for 1 hour. Washed and filtered. The filtrate was dried at 70 ° C. overnight.
- Example 1-8 (Synthesis of a solid catalyst in which gold is immobilized on manganese dioxide (hereinafter also referred to as “Au / MnO 2 ”)) 110 mg of tetrachloroauric acid tetrahydrate was dissolved in 180 mL of distilled water, and 3.2 g of urea and 1 g of manganese dioxide (average primary particle size 40 nm) were added in this order at room temperature. Thereafter, the solution was gradually warmed to 90 ° C. and stirred at 90 ° C. for 18 hours. The precipitate was washed with distilled water and filtered. The obtained filtrate was dried at 65 ° C. overnight.
- the solid catalyst (Au / MnO 2 ) in which gold was immobilized on manganese dioxide was obtained by firing in air at 300 ° C. for 4 hours.
- the average primary particle size of the obtained solid catalyst was about 40 nm, the amount of gold immobilized was 4% by mass, and the average particle size of gold particles on the support was 5 nm.
- Example 1-9 Synthesis of a solid catalyst in which gold is immobilized on zirconium oxide (hereinafter also referred to as “Au / ZrO 2 ”) 22 mg of tetrachloroauric acid tetrahydrate was dissolved in 52 mL of distilled water, and while the solution was heated to 70 ° C., an aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7. 1 g of zirconium oxide (manufactured by Daiichi Rare Element Chemical Co., Ltd., RC-100 (trade name), average primary particle size 5 nm) was added to the solution after adjustment, and then the mixture was stirred at 70 ° C.
- Cobalt oxide was obtained by calcining 11 g of basic cobalt carbonate in air at 300 ° C. for 4 hours.
- Example 1-12 (Synthesis of a solid catalyst in which gold is immobilized on cobalt oxide (hereinafter also referred to as “Au / Co 3 O 4 ”)) Dissolve 470 mg of tetrachloroauric acid tetrahydrate in 66 mL of distilled water, add 2.0 g of cobalt oxide prepared in Reference Example 1-10 at room temperature, and add aqueous sodium hydroxide solution dropwise to adjust the pH to 7. While stirring at room temperature. After 3 hours, the precipitate was washed with distilled water and filtered. The obtained filtrate was dried at 65 ° C. overnight.
- the solid catalyst (Au / Co 3 O 4 ) in which gold was immobilized on cobalt oxide by a precipitation method was obtained by firing in air at 300 ° C. for 4 hours.
- the amount of gold immobilized in the obtained solid catalyst was 7% by mass.
- Example 1-13 Synthesis of solid catalyst having gold immobilized on lanthanum oxide (hereinafter also referred to as “Au / La 2 O 3 ”))
- Lanthanum nitrate (III) hexahydrate 8.2 g and tetrachloroauric acid tetrahydrate 0.41 g were dissolved in distilled water 200 mL at room temperature (aqueous solution 9).
- aqueous solution 9 Lanthanum nitrate (III) hexahydrate 8.2 g and tetrachloroauric acid tetrahydrate 0.41 g were dissolved in distilled water 200 mL at room temperature (aqueous solution 9).
- aqueous solution 10 3.9 g of sodium carbonate was dissolved in 366 mL of distilled water.
- the aqueous solution 9 was added to the aqueous solution 10 at once, and the mixed solution was stirred at 70 ° C. for 1.5 hours.
- the produced precipitate was washed with distilled water and filtered until the pH became constant. The filtrate was dried at 80 ° C. overnight. After drying, the solid catalyst (Au / La 2 O 3 ) in which gold was immobilized on lanthanum oxide was obtained by firing in air at 300 ° C. for 4 hours. The amount of gold immobilized in the obtained solid catalyst was 6% by mass.
- Example 1-14 (Synthesis of a solid catalyst in which gold is immobilized on aluminum oxide (hereinafter also referred to as “Au / Al 2 O 3 ”)) 173 mg of tetrachloroauric acid tetrahydrate and 25 g of urea are dissolved in 100 mL of distilled water, and 1.0 g of aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd., AKP-G015 (trade name), particle size less than 100 nm) is dissolved in this solution. Was added at room temperature. Thereafter, the solution was gradually heated to 80 ° C. and stirred at 80 ° C. for 8 hours.
- Al oxide manufactured by Sumitomo Chemical Co., Ltd., AKP-G015 (trade name), particle size less than 100 nm
- the precipitate was washed 5 times with distilled water and filtered. The obtained filtrate was dried at 80 ° C. overnight. After drying, the solid catalyst (Au / Al 2 O 3 ) in which gold was immobilized on aluminum oxide was obtained by firing in air at 300 ° C. for 4 hours. The primary particle diameter of the obtained solid catalyst was less than 100 nm, and the amount of gold immobilized was 8% by mass.
- Example 1-15 Synthesis of a solid catalyst having gold immobilized on zirconium oxide (hereinafter also referred to as “Au / ZrO 2 ”) 173 mg of tetrachloroauric acid tetrahydrate and 25 g of urea are dissolved in 100 mL of distilled water. 5 nm) 1.0 g was added at room temperature. Thereafter, the solution was gradually heated to 80 ° C. and stirred at 80 ° C. for 8 hours. After cooling to 50 ° C., the precipitate was washed 5 times with distilled water and filtered. The obtained filtrate was dried at 80 ° C. overnight. After drying, calcination was performed in air at 300 ° C.
- Example 1-16 (Synthesis of a solid catalyst having gold immobilized on zirconium oxide (hereinafter also referred to as “Au / ZrO 2 ”)) 173 mg of tetrachloroauric acid tetrahydrate and 2.5 g of urea were dissolved in 100 mL of distilled water. 1.0 g (particle size 5 nm) was added at room temperature. Thereafter, the solution was gradually warmed to 90 ° C. and stirred at 90 ° C. for 4 hours. After cooling to room temperature, the precipitate was washed 5 times with distilled water and filtered. The obtained filtrate was dried at 70 ° C. overnight. After drying, calcination was performed in air at 300 ° C.
- Example 1-17 (Synthesis of a solid catalyst in which gold is immobilized on titanium oxide (hereinafter also referred to as “Au / TiO 2 ”)) 173 mg of tetrachloroauric acid tetrahydrate and 25 g of urea were dissolved in 100 mL of distilled water, and titanium oxide (Nippon Aerosil Co., Ltd., P-25 (trade name), average primary particle size 25 nm) was dissolved in this solution. 0 g was added at room temperature. Thereafter, the solution was gradually heated to 80 ° C. and stirred at 80 ° C. for 8 hours. After cooling to 50 ° C., the precipitate was washed 5 times with distilled water and filtered.
- Au / TiO 2 titanium oxide
- the obtained filtrate was dried at 80 ° C. overnight. After drying, calcination was performed in air at 300 ° C. for 4 hours to obtain a solid catalyst (Au / TiO 2 ) in which gold was immobilized on titanium oxide.
- the average primary particle size of the obtained solid catalyst was about 25 nm, and the amount of gold immobilized was 8% by mass.
- Example 1-18 Synthesis of a solid catalyst in which gold is immobilized on cerium oxide (hereinafter also referred to as “Au / CeO 2 ”)) 173 mg of tetrachloroauric acid tetrahydrate and 25 g of urea were dissolved in 100 mL of distilled water, and cerium oxide (manufactured by Daiichi Elemental Chemical Co., Ltd., JRC-CEO-3 (trade name), average primary) was dissolved in this solution. 1.0 g (particle diameter 11 nm) was added at room temperature. Thereafter, the solution was gradually heated to 80 ° C. and stirred at 80 ° C. for 8 hours.
- Au / CeO 2 cerium oxide
- Example 1-19 (Synthesis of a solid catalyst in which gold is immobilized on cerium oxide (hereinafter also referred to as “Au / CeO 2 ”)) 173 mg of tetrachloroauric acid tetrahydrate and 25 g of urea are dissolved in 100 mL of distilled water. 8 nm) 1.0 g was added at room temperature. Thereafter, the solution was gradually heated to 80 ° C. and stirred at 80 ° C. for 8 hours. After cooling to 50 ° C., the precipitate was washed 5 times with distilled water and filtered. The obtained filtrate was dried at 80 ° C. overnight. After drying, the filtered product is packed in a U-shaped reaction tube and heated to 200 ° C.
- Example 1-20 Synthesis of solid catalyst in which gold is immobilized on dimanganese trioxide (hereinafter also referred to as “Au / Mn 2 O 3 ”)) Dissolve 220 mg of tetrachloroauric acid tetrahydrate in 360 mL of distilled water, and add 6.4 g of urea and 2 g of dimanganese trioxide (manufactured by Aldrich Co., Ltd., average primary particle size of 40 nm) in this order. At room temperature. Thereafter, the solution was gradually warmed to 90 ° C. and stirred at 90 ° C. for 18 hours. The precipitate was washed with distilled water and filtered.
- the obtained filtrate was dried at 65 ° C. overnight.
- the solid catalyst (Au / Mn 2 O 3 ) in which gold was immobilized on dimanganese trioxide was obtained by performing calcination in air at 300 ° C. for 4 hours.
- the average primary particle size of the obtained solid catalyst was about 40 nm, the amount of gold immobilized was 4% by mass, and the average particle size of the gold particles on the support was 9 nm.
- Example 1-22 Synthesis of solid catalyst having gold immobilized on manganese dioxide (hereinafter also referred to as “Au / MnO 2 ”) 220 mg of tetrachloroauric acid tetrahydrate was dissolved in 360 mL of distilled water, and 6.4 g of urea and 2 g of manganese dioxide prepared in Reference Example 1-21 were sequentially added at room temperature. Thereafter, the reaction solution was gradually heated to 90 ° C., and heated and stirred at 90 ° C. for 18 hours. The precipitate was washed with distilled water and filtered. The obtained filtrate was dried at 65 ° C. overnight. After drying, the solid catalyst (Au / MnO 2 ) in which gold was immobilized on manganese dioxide was obtained by firing in air at 300 ° C. for 4 hours. The amount of gold immobilized on the obtained solid catalyst was 5% by mass.
- Reference Example 1-23 Preparation of cerium oxide doped with lanthanum (hereinafter also referred to as “Ce (La) O 2 ”)) 12 g of ammonium hexanitratocerium (IV), 1.1 g of lanthanum nitrate hexahydrate, and 24 g of urea were dissolved in 200 mL of distilled water, and this solution was stirred under reflux. After 8 hours, the precipitate was washed with distilled water and filtered. The filtrate was dried at 80 ° C. After drying, cerium oxide doped with lanthanum (Ce (La) O 2 ) was obtained by baking in air at 400 ° C. for 7 hours. The average primary particle diameter of the obtained cerium oxide doped with lanthanum was 4 nm.
- Reference Example 1-24 ( Preparation of zirconium-doped cerium oxide (hereinafter also referred to as “Ce (Zr) O 2 ”)) 12 g of ammonium hexanitratocerium (IV), 0.7 g of zirconium nitrate, and 24 g of urea were dissolved in 200 mL of distilled water, and this solution was stirred under reflux. After 8 hours, the precipitate was washed with distilled water and filtered. The filtrate was dried at 80 ° C. After drying, cerium oxide doped with zirconium (Ce (Zr) O 2 ) was obtained by baking in air at 400 ° C. for 7 hours. The average primary particle size of the obtained zirconium-doped cerium oxide was 4 nm.
- Example 1-25 Synthesis of a solid catalyst in which gold is immobilized on cerium oxide doped with lanthanum (hereinafter also referred to as “Au / Ce (La) O 2 ”)
- Tetrachloroauric acid / tetrahydrate 43 mg was dissolved in distilled water (100 mL), and while heating to 70 ° C., an aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7-8.
- 1 g of Ce (La) O 2 prepared in Reference Example 1-23 was added, and then stirred at 70 ° C. After 1 hour, the precipitate was washed with distilled water and filtered until the pH became constant. The filtrate was dried at 80 ° C. overnight.
- the solid catalyst Au / Ce (La) O 2
- gold was immobilized on cerium oxide doped with lanthanum was obtained by reduction at 300 ° C. under hydrogen.
- the average primary particle size of the obtained solid catalyst was 4 nm
- the amount of gold immobilized was 1% by mass
- the average particle size of gold particles on the support was 3 nm.
- Example 1-26 Synthesis of a solid catalyst in which gold is immobilized on cerium oxide doped with zirconium (hereinafter also referred to as “Au / Ce (Zr) O 2 ”)
- Tetrachloroauric acid / tetrahydrate 43 mg was dissolved in distilled water (100 mL), and while heating to 70 ° C., an aqueous sodium hydroxide solution was added dropwise to adjust the pH of the solution to 7-8.
- 1 g of Ce (Zr) O 2 prepared in Reference Example 1-23 was added thereto, and then stirred at 70 ° C. After 1 hour, the precipitate was washed with distilled water and filtered until the pH became constant. The filtrate was dried at 80 ° C. overnight.
- Example 1-27 (Catalyst regeneration) In a three-necked flask with an internal volume of 25 mL, 3.5 g (18 mmol) of dimethyl o-phthalate, 1.9 g of Au / Co 3 O 4 prepared in Example 1-1 (6 mol% with respect to dimethyl o-phthalate), And 7 mL of acetic acid was introduced. The reaction vessel was immersed in an oil bath set at 125 ° C. in advance, reacted for 72 hours, and analyzed. As a result, 3,3 ′, 4,4′-biphenyltetracarboxylic acid tetramethyl ester (s -DM) was produced in a yield of 11%.
- s -DM 3,3 ′, 4,4′-biphenyltetracarboxylic acid tetramethyl ester
- the reaction was further continued for 24 hours, and the yield was 11% unchanged. Thus, it was confirmed that the reaction had stopped.
- the precipitate was filtered and the filtrate was washed with acetone.
- the washed filtrate was dried at 100 ° C. under reduced pressure to obtain a solid catalyst (Au / Co 3 O 4 ) in which gold was immobilized on cobalt oxide.
- This solid was calcined at 300 ° C. in the air for 4 hours to obtain a calcined solid catalyst (Au / Co 3 O 4 ).
- the particle size of the obtained solid catalyst was 5 to 20 nm, and the average particle size of the gold particles on the support was 8 nm.
- Example 2-1 Synthesis of biphenyltetracarboxylic acid ester
- SUS autoclave internal volume 50 mL
- glass intubation tube 0.27 g (1.4 mmol) of dimethyl o-phthalate and 0.10 g of Au / Co 3 O 4 prepared in Example 1-1 (o- 4 mol% with respect to dimethyl phthalate) and 2.7 mL of acetic acid were introduced. Thereafter, air was injected so that the pressure in the reaction system was 2.5 MPa. Next, the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-2 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 50 mL
- 0.23 g (1.2 mmol) of dimethyl o-phthalate and 0.15 g of Au / Co 3 O 4 prepared in Example 1-1 (o- 7 mol% with respect to dimethyl phthalate) and 0.8 mL of acetic acid were introduced.
- nitrogen gas was injected so that the pressure in the reaction system was 1.0 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-3 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 50 mL
- a glass intubation 2.78 g (14.3 mmol) of dimethyl o-phthalate and 26 mg of Au / Co 3 O 4 prepared in Example 1-1 (o-phthalate) 0.1 mol% with respect to dimethyl acid.
- Air was injected so that the pressure in the reaction system was 2.5 MPa.
- the autoclave was immersed in an oil bath set at 150 ° C. in advance and reacted for 40 hours. Further, the oil bath was heated to 200 ° C. and reacted for 20 hours.
- Example 2-4 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g 1.0 mmol
- dimethyl o-phthalate 0.20 g
- Au / Co 3 O 4 prepared in Example 1-1 (o-phthalic acid) 4 mol% with respect to dimethyl
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C.
- Example 2-5 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g 1.0 mmol
- dimethyl o-phthalate 0.20 g
- 74 mg of Au / Co 3 O 4 prepared in Example 1-1 o-phthalic acid 4 mol% relative to dimethyl
- butyric acid 0.5 mL
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-6 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g 1.0 mmol
- dimethyl o-phthalate 0.20 g
- 74 mg of Au / Co 3 O 4 prepared in Example 1-1 o-phthalic acid 4 mol% relative to dimethyl
- isovaleric acid 0.5 mL
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-7 Synthesis of biphenyltetracarboxylic acid ester
- Into a 10 mL glass Schlenk tube 0.20 g (1.0 mmol) of dimethyl o-phthalate, 74 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to dimethyl o-phthalate), And 0.4 mL of propionic acid was introduced. After replacing the inside of the reaction system with nitrogen gas at normal pressure, the Schlenk tube was immersed in an oil bath set at 150 ° C. in advance and reacted for 34 hours. After completion of the reaction, the Schlenk tube was air-cooled to release the gas in the Schlenk tube.
- Example 2-8 (Synthesis of biphenyltetracarboxylic acid ester) Into a 10 mL glass Schlenk tube, 0.20 g (1.0 mmol) of dimethyl o-phthalate, 73 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to dimethyl o-phthalate), And 0.4 mL of acetic acid was introduced. After substituting the inside of the reaction system with nitrogen gas at normal pressure, the Schlenk tube was immersed in an oil bath set at 125 ° C. in advance and reacted for 67 hours. After completion of the reaction, the Schlenk tube was air-cooled to release the gas in the Schlenk tube.
- Example 2-9 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g 1.0 mmol
- dimethyl o-phthalate 100 mg
- Au / NiO prepared in Example 1-2 100 mg
- 0.4 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-10 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.20 mg
- 0.4 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-11 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.15 g of Au / CeO 2 prepared in Example 1-4 (o-phthalic acid) 0.8 mol% with respect to dimethyl) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-12 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.15 g of Au / TiO 2 prepared in Example 1-5 (o-phthalic acid) 0.8 mol% with respect to dimethyl) and 0.4 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-13 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g 1.0 mmol
- 0.20 g of Au / Co / SiO 2 prepared in Example 1-6 o- 5 mol% with respect to dimethyl phthalate
- 0.4 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-14 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.40 g of Au / Co 3 O 4 —CeO 2 prepared in Example 1-7 (2 mol% with respect to dimethyl o-phthalate) and 0.7 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-15 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.15 g of Au / ZrO 2 prepared in Example 1-9 (o-phthalic acid) 0.8 mol% with respect to dimethyl) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-16 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate 0.15 g of Au / Co 3 O 4 -CeO 2 prepared in Example 1-7 (o -0.75 mol% with respect to dimethyl phthalate) and 0.5 mL of acetic acid.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-17 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction vessel having an internal volume of 30 mL
- 0.20 g (1.0 mmol) of dimethyl o-phthalate 0.20 g (1.0 mmol) of dimethyl o-phthalate, 70 mg of Au / Co 3 O 4 prepared by the precipitation method in Example 1-12 (o-phthalic acid) 4 mol% relative to dimethyl) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block set at 125 ° C. in advance under normal pressure under air and reacted for 24 hours. After completion of the reaction, the reaction solution was air-cooled.
- Example 2-18 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g 1.0 mmol
- dimethyl o-phthalate 0.13 g
- Au / La 2 O 3 prepared in Example 1-13 o— 4 mol% relative to dimethyl phthalate
- 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-19 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / Al 2 O 3 prepared in Example 1-14 (o-phthalic acid) 4 mol% relative to dimethyl) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.6 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-20 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume of 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / ZrO 2 prepared in Example 1-15 (to dimethyl o-phthalate) 4 mol%) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.85 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-21 Synthesis of biphenyltetracarboxylic acid ester
- SUS autoclave internal volume of 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / ZrO 2 prepared in Example 1-16 (to dimethyl o-phthalate) 4 mol%) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.85 MPa.
- the autoclave was immersed in an oil bath set at 140 ° C. in advance and reacted for 48 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the autoclave.
- Example 2-22 Synthesis of biphenyltetracarboxylic acid ester
- SUS autoclave internal volume of 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / TiO 2 prepared in Example 1-17 (to dimethyl o-phthalate) 4 mol%) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.6 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and reacted for 72 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-23 Synthesis of biphenyltetracarboxylic acid ester
- SUS autoclave internal volume of 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / CeO 2 prepared in Example 1-18 (to dimethyl o-phthalate) 4 mol%) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.6 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation.
- Example 2-24 Synthesis of biphenyltetracarboxylic acid ester
- a SUS autoclave internal volume 30 mL
- 0.20 g (1 mmol) of dimethyl o-phthalate and 0.10 g of Au / CeO 2 prepared in Example 1-19 (to dimethyl o-phthalate) 4 mol%) and 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the autoclave.
- Example 2-25 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction vessel with an internal volume of 30 mL 0.20 g (1.0 mmol) of dimethyl o-phthalate, 0.21 g of Au / Mn 2 O 3 prepared by the precipitation method in Example 1-20 (o— 6 mol% with respect to dimethyl phthalate) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block set at 125 ° C. in advance under normal pressure under air to cause a reaction.
- Example 2-26 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction vessel with an internal volume of 30 mL 0.20 g (1.0 mmol) of dimethyl o-phthalate, 71 mg of Au / MnO 2 prepared using the precipitation method in Example 1-22 (into dimethyl o-phthalate) 4 mol%) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block that had been set to 125 ° C. in advance under normal pressure under air and reacted for 48 hours. After completion of the reaction, the reaction solution was air-cooled.
- Example 2-27 Synthesis of biphenyltetracarboxylic acid ester by regenerated solid catalyst
- a glass reaction vessel with an internal volume of 30 mL, 0.10 g (0.5 mmol) of dimethyl o-phthalate and 36 mg of Au / Co 3 O 4 fired in Example 1-27 (based on dimethyl o-phthalate) 4 mol%) and 0.2 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block previously set at 125 ° C. under normal pressure under air and reacted for 41 hours. After completion of the reaction, the reaction solution was air-cooled.
- Example 2-30 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction container having an internal volume of 2 mL, 0.40 g (2.1 mmol) of dimethyl o-phthalate and 0.144 g of Au / Co 3 O 4 prepared using the precipitation method in Example 1-12 (o -4 mol% with respect to dimethyl phthalate).
- Example 2-31 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction vessel with an internal volume of 30 mL
- 0.4 mol%) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block that had been set to 125 ° C. in advance, and reacted for 100 hours.
- the reaction solution obtained by air cooling was analyzed by gas chromatography.
- Example 2-32 Synthesis of biphenyltetracarboxylic acid ester
- a glass reaction vessel having an internal volume of 30 mL
- 0.4 mol%) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block that had been set to 125 ° C. in advance and reacted for 48 hours.
- the reaction solution obtained by air cooling was analyzed by gas chromatography.
- Example 2-33 Synthesis of biphenyltetracarboxylic acid ester
- 0.20 g (1.0 mmol) of dimethyl o-phthalate, 85 mg of Au / TiO 2 prepared in Example 1-5 (o-phthalic acid) 0.4 mol% of gold relative to dimethyl) and 0.2 mL of 1H, 1H-tridecafluoro-1-heptanol were introduced. Air was injected so that the pressure in the reaction system was 2.5 MPa. Next, the autoclave was immersed in an oil bath set at 150 ° C. in advance and reacted for 24 hours.
- Example 2-34 Synthesis of biphenyltetracarboxylic acid ester
- 0.20 g (1.0 mmol) of dimethyl o-phthalate, 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (o— 4 mol% of gold with respect to dimethyl phthalate) and 0.3 mL of 1H, 1H-tridecafluoro-1-heptanol were introduced. Air was injected so that the pressure in the reaction system was 2.5 MPa. Next, the autoclave was immersed in an oil bath set at 150 ° C. in advance and reacted for 16 hours.
- Example 2-35 Synthesis of 3,3 ′, 4,4′-tetramethylbiphenyl
- a SUS autoclave (internal volume of 50 mL) with glass intubation, 0.11 g (1.0 mmol) of o-xylene and 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol with respect to o-xylene) %), And 0.4 mL of acetic acid were introduced. After replacing the inside of the reaction system with nitrogen gas, nitrogen gas was injected so that the pressure in the reaction system was 0.5 MPa. Next, the autoclave was immersed in an oil bath set at 125 ° C. in advance and reacted for 24 hours.
- Example 2-36 Synthesis of 3,3 ′, 4,4′-tetramethylbiphenyl
- 0.11 g (1.0 mmol) of o-xylene and 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol with respect to o-xylene) %), And 0.4 mL of acetic acid were introduced.
- the heating unit was set to 125 ° C. in advance and reacted for 51 hours.
- the reaction solution obtained by air cooling was analyzed by gas chromatography. As a result, 3,3 ′, 4,4′-tetramethylbiphenyl was produced in a yield of 7.5%.
- Example 2-37 Synthesis of dimethyl 4,4'-biphenyldicarboxylate
- 0.14 g 1.0 mmol
- 72 mg of Au / Co 3 O 4 prepared in Example 1-1 4 mol with respect to methyl benzoate
- 0.4 mL of acetic acid were introduced.
- the heating unit was set to 125 ° C. in advance and reacted for 51 hours.
- the reaction solution obtained by air cooling was analyzed by gas chromatography. As a result, dimethyl 4,4′-biphenyldicarboxylate was produced in a yield of 3.3%.
- Example 2-38 Synthesis of 4,4'-dimethylbiphenyl
- 0.09 g (1.0 mmol) of toluene, 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to toluene), and Acetic acid 0.4 mL was introduced.
- nitrogen gas was injected so that the pressure in the reaction system was 0.5 MPa.
- the autoclave was immersed in an oil bath set in advance at 125 ° C. and reacted for 25 hours.
- FIG. 1 A gas chromatography chart is shown in FIG. In the gas chromatography chart (FIG. 1), six types of peaks corresponding to toluene dimer (dimethylbiphenyl) are observed, of which peaks observed at a position of 15.9 minutes are 4,4 It was a peak of '-dimethylbiphenyl.
- Example 2-39 Synthesis of benzoic acid dimer
- 0.12 g (1.0 mmol) of benzoic acid and 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to benzoic acid) was introduced.
- the heating unit was set to 125 ° C. in advance and reacted for 51 hours.
- the reaction solution obtained by air cooling was analyzed by high performance liquid chromatography (HPLC).
- HPLC high performance liquid chromatography
- Example 2-40 (Synthesis of tetramethylbiphenyl) In an SUS autoclave (internal volume 50 mL) with a glass intubation tube, 0.52 g (4.9 mmol) of xylene (a mixture of o-, m-, and p-isomers), and Au / prepared in Example 1-8 0.15 g of MnO 2 (0.8 mol% with respect to xylene) was introduced. Oxygen gas was injected so that the pressure in the reaction system was 0.5 MPa. Next, the autoclave was immersed in an oil bath set at 100 ° C. in advance and reacted for 19 hours. After completion of the reaction, the autoclave was air-cooled and the gas was released from the glass intubation. When the obtained reaction liquid was analyzed by gas chromatography using gas chromatography, it was confirmed that xylene dimer (tetramethylbiphenyl) was formed.
- xylene dimer tetramethylbiphenyl
- Example 2-41 (Synthesis of tetramethylbiphenyl) In a Pyrex (registered trademark) glass vial with an internal volume of 13 mL, 0.11 g (1 mmol) of o-xylene, 74 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to o-xylene), And 0.5 mL of acetic acid was introduced.
- Example 2-42 Synthesis of 4,4'-bistrifluoromethylbiphenyl
- a SUS autoclave (internal volume 30 mL) with glass intubation, 0.15 g (1 mmol) of trifluoromethylbenzene, 74 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol with respect to trifluoromethylbenzene) %), And 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.6 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and allowed to react for 18 hours.
- Example 2-43 (Synthesis of 2,2 ', 5,5'-tetramethoxybiphenyl) In a Pyrex (registered trademark) glass vial with an internal volume of 13 mL, 0.14 g (1 mmol) of p-dimethoxybenzene and 74 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to p-dimethoxybenzene) ), And 0.5 mL of acetic acid were introduced.
- the reaction vessel was immersed in an oil bath set in advance at 150 ° C. under normal pressure under air and allowed to react for 18 hours. After completion of the reaction, the reaction solution was air-cooled. When the obtained reaction solution was analyzed by gas chromatography, 2,2 ′, 5,5′-tetramethoxybiphenyl was produced in a yield of 21%.
- Example 2-44 Synthesis of di-tert- butylbiphenyl .
- SUS autoclave internal volume 30 mL
- 0.5 mL of acetic acid were introduced.
- Oxygen gas was injected so that the pressure in the reaction system was 1.6 MPa.
- the autoclave was immersed in an oil bath set in advance at 150 ° C. and reacted for 66 hours.
- Example 2-45 Synthesis of 3,3 ′, 4,4′-tetramethoxybiphenyl
- a glass reaction container having an internal volume of 30 mL
- 0.14 g (1.0 mmol) of o-dimethoxybenzene, 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (4 mol% with respect to o-dimethoxybenzene), and Acetic acid 0.4 mL was introduced.
- the reaction vessel was brought into contact with an aluminum block set at 125 ° C. in advance under normal pressure under air and reacted for 15 hours. After completion of the reaction, the reaction solution was air-cooled.
- 3,3 ′, 4,4′-tetramethoxybiphenyl was produced in a yield of 19%.
- Example 2-46 (Synthesis of 2,2 ′, 3,3 ′, 5,5′-hexamethyl- [biphenyl] -4,4′-diol)
- a glass reaction vessel with an internal volume of 30 mL
- 0.14 g (1.0 mmol) of 2,3,6-trimethylphenol and 72 mg of Au / Co 3 O 4 prepared in Example 1-1 (2,3,6-trimethyl) 4 mol% relative to phenol) and 0.4 mL of acetic acid were introduced.
- the reaction vessel was brought into contact with an aluminum block that had been set to 125 ° C. at normal pressure under air and reacted for 22 hours. After completion of the reaction, the reaction solution was air-cooled.
- 2,2 ′, 3,3 ′, 5,5′-hexamethyl- [biphenyl] -4,4′-diol was produced in a yield of 46%. It was.
- Comparative Example 2-2 Gold dissolution experiment
- a glass reaction container having an internal volume of 10 mL
- 75 mg of Au / Co 3 O 4 prepared in Example 1-1 and 0.4 mL of acetic acid were introduced.
- the reaction vessel was immersed in an oil bath set at 125 ° C. in a nitrogen gas atmosphere at normal pressure and heated and stirred for 1 hour.
- the solution was filtered while hot, and the filtrate was washed with 3 mL of acetic acid heated to 125 ° C.
- ICP-AES ICP-AES
- Example 3-1 Synthesis of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- a titanium autoclave with an internal volume of 100 mL 2.10 g (10 mmol) of 3,3 ′, 4,4′-tetramethylbiphenyl synthesized in Example 2-15, 12.4 mg (0.05 mmol) of cobalt acetate tetrahydrate. ), 12.2 mg (0.05 mmol) of manganese acetate tetrahydrate, 163 mg (1 mmol) of N-hydroxyphthalimide (hereinafter referred to as “NHPI”), and 15 mL of acetic acid were introduced in an air atmosphere (internal pressure 3 MPa).
- NHPI N-hydroxyphthalimide
- the reaction was performed at 150 ° C. One hour after the start of the reaction, the autoclave was cooled to room temperature, and the gas in the autoclave was released. After further adding 163 mg of NHPI into the autoclave, the reaction was resumed at 150 ° C. After 1 hour, this series of operations (cooling-gas release-addition-reaction restart) was repeated, and the reaction was conducted for a total of 3 hours. After completion of the reaction, the autoclave was cooled to room temperature, and the gas in the autoclave was released.
- the solvent was distilled off from the obtained reaction liquid, and ethyl acetate and water were added thereto for liquid separation, and then the ethyl acetate layer was washed with water to remove the metal compound, and 3,3 ′, 4,4 ′.
- -Biphenyltetracarboxylic dianhydride was obtained.
- Tables 2 to 10 summarize the coupling reaction conditions and the analysis results of the products in Examples 2-1 to 2-47 and Comparative Examples 2-1 to 2-5.
- the numerical value shown in parentheses in the column of solid catalyst is the ratio of the number of moles of gold immobilized on the carrier to the total number of moles of the substituted benzene compound (the number of equivalents of the solid catalyst). Show.
- the numerical values shown in parentheses for tetrachloroauric acid tetrahydrate of Comparative Example 2-1 are the moles of tetrachloroauric acid tetrahydrate relative to the total number of moles of the substituted benzene compound. Indicates the ratio of numbers.
- the production method and solid catalyst of the polyvalent substituted biphenyl compound of the present invention can be applied to, for example, production of a monomer having a biphenyl skeleton, which is a raw material of polyimide, and production of a basic skeleton of liquid crystal molecules.
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Abstract
Description
本実施形態の固体触媒は、担体に金が物理的又は化学的に固定化(「担持」ということもある)されたものである。なお、以下に記載する、固体触媒の一次粒径は、固体触媒を形成する一つ一つの粒子(一次粒子)の粒径を表す。また、金粒子の粒子径は、固体触媒上に固定化された一つ一つの金粒子の粒子径を表す。
担体である金属酸化物の前駆体となる当該金属の硝酸塩と金化合物とを含む水溶液を、塩基性化合物の水溶液に加えて中和することにより、当該金属の炭酸塩又は水酸化物とともに金の水酸化物を沈殿させる。沈殿物を水洗し、乾燥後、任意の雰囲気で焼成することにより、金が固定化された固体触媒を得ることができる。
塩基性化合物を加えてpHを7~10の範囲に調整した金化合物の水溶液に、担体である酸化物の粉末、又は上記粉末を球状、円筒状及び蜂の巣(ハニカム)状などの支持体に担持させた成形体を懸濁又は浸漬させ、金の水酸化物を酸化物担体の表面上に析出沈殿させる。金の水酸化物が析出沈殿した担体を水洗し、乾燥後、任意の雰囲気で焼成することにより、金が固定化された固体触媒を得ることができる。前述の塩基性化合物は、調製する固体触媒に応じて適宜選択され、たとえば、水酸化ナトリウム及び尿素等が用いられる。
本実施形態のカップリング反応において基質として使用される置換ベンゼン化合物は、下記一般式(1)で表される化合物である。
本実施形態の多価置換ビフェニル化合物の製造方法では、溶媒の存在下で、置換ベンゼン化合物同士をカップリングさせてもよい。
本実施形態の置換ベンゼン化合物のカップリング反応は、上記固体触媒及び上記置換ベンゼン化合物を、必要に応じて溶媒を混合して、攪拌しながら反応させる等の方法によって行われる。カップリング反応の温度は、好ましくは50~250℃、より好ましくは100~200℃であり、反応圧力は、好ましくは0.1~5MPa、より好ましくは0.1~2.5MPaである。なお、反応形態は、バッチ又は流通、気相又は液相、固定床又は流動床のいずれの形態でも構わない。
本実施形態の製造方法により得られる多価置換ビフェニル化合物は下記一般式(2)で表される構造を有する。
TEMにより、担体及び固体触媒の一次粒子、並びに担体上の金粒子を観察し、TEM写真中の粒子に外接する円(外接円)の直径を測定し、当該直径をそれぞれ担体及び固体触媒の一次粒径、並びに担体上の金粒子の粒子径とした。任意に選択した10個以上の粒子の粒径を測定し、粒径分布を作成することにより、担体、固体触媒及び担体上の金粒子の個数平均径を算出した。算出した個数平均径を、それぞれ、担体及び固体触媒の平均一次粒径、並びに金粒子の平均粒子径とした。なお、TEM写真において、エネルギー分散型X線分光(EDS)測定をすることにより、担体上の金粒子を特定した。
固体触媒を王水で加温溶解させ、超純水で希釈した。誘導プラズマ発光分光分析法(ICP-AES)により、上記液中に溶解する金の発光強度を測定した。上記液中に溶解する金の発光強度と、金の濃度が既知の標準溶液中の金の発光強度とを比較することにより、上記液中の金の溶解量を算出した。上記溶解量から、固体触媒の単位質量中に含まれる金の含有量、すなわち金の固定化量(質量%)を算出した。
反応生成物の同定及び生成量の測定は、特に断りのない限り、ガスクロマトグラフィー(FID検出器)を用いて、反応生成物と標準物質の保持時間及びピーク強度を比較することにより行った。測定条件は以下のとおりである。
装置:アジレント・テクノロジー製 Agilent 6850 SeriesII
カラム:J&W Scientific社製 HP-1(内径:0.32mm、長さ:30m、膜厚:0.25μm)
キャリアガス:ヘリウム 120kPa
昇温条件:10℃/分で40℃から280℃まで昇温し、280℃で10分間保持した。
置換ベンゼン化合物(基質)として、たとえば、o-フタル酸ジメチルを用いた場合の生成物(ビフェニルテトラカルボン酸テトラメチルエステル)には、以下の二種類の生成物が主な異性体として存在する。以下、3,3’,4,4’-ビフェニルテトラ酢酸テトラメチルエステルを「s-DM」(s-体)、2,3,3’,4’-ビフェニルテトラ酢酸テトラメチルエステルを「a-DM」(а-体)ということがある。
収率(mol%)=2×Ms×100/Mf
生成比(s/a比)=Ms/Ma
担体として金属酸化物(MeyOz)を用いてカップリング反応を行う場合の、固体触媒の当量数(担体に固定化された金の基質に対するmol%)を、下記式により算出した。
固体触媒の当量数(mol%)=(100×b×c)/{d×(a/y×e+b×197)}
Me:担体の金属原子
O:酸素原子
y,z:それぞれ金属酸化物中のMe、Oの数を表す数値
a:固体触媒調製時に使用する担体を構成する金属酸化物のモル数(mol)
b:固体触媒調製時に使用する金化合物のモル数(mol)
c:カップリング反応時に使用する固体触媒の質量(g)
d:カップリング反応時に使用する基質のモル数(mol)
e:金属酸化物(MeyOz)のモル質量(g)
硝酸コバルト(II)・六水和物5.52g、及びテトラクロロ金酸・四水和物0.41gを蒸留水200mLに室温で溶解させた(水溶液1)。一方、これとは別に炭酸ナトリウム2.63gを蒸留水200mLに溶解させた(水溶液2)。次いで、上記水溶液1を上記水溶液2に一気に添加し、混合液を室温で3時間撹拌した。生成した沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を70℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化コバルトに金が固定化された固体触媒(Au/Co3O4)を得た。得られた固体触媒の平均一次粒径は約15nmであり、金の固定化量は10質量%であり、担体上の金粒子の平均粒子径は2nmであった。
硝酸ニッケル・六水和物5.53g、及びテトラクロロ金酸・四水和物0.41gを蒸留水200mLに室温で溶解させ、70℃に加温した(水溶液3)。一方、これとは別に炭酸ナトリウム2.67gを蒸留水250mLに溶解させ、70℃に加温した(水溶液4)。次いで、上記水溶液3を上記水溶液4に一気に添加し、混合液を70℃で1時間撹拌した。生成した沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を70℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化ニッケルに金が固定化された固体触媒(Au/NiO)を得た。得られた固体触媒の平均一次粒径は約5nmであり、金の固定化量は10質量%であり、担体上の金粒子の平均粒子径は4nmであった。
硝酸鉄(II)・九水和物7.68g、及びテトラクロロ金酸・四水和物0.41gを蒸留水200mLに室温で溶解させた(水溶液5)。一方、これとは別に炭酸ナトリウム3.88gを蒸留水370mLに溶解させ、70℃に加温した(水溶液6)。次いで、上記水溶液5を上記水溶液6に一気に添加し、混合液を70℃で1時間撹拌した。生成した沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化鉄に金が固定化された固体触媒(Au/Fe2O3)を得た。得られた固体触媒の平均一次粒径は約20nmであり、金の固定化量は9質量%であり、担体上の金粒子の平均粒子径は4nmであった。
テトラクロロ金酸・四水和物64mgを蒸留水155mLに溶解させ、70℃に加温しながら、水酸化ナトリウム水溶液を滴下して、溶液のpHを7に調整した。これに酸化セリウム(第一稀元素化学工業(株)製、酸化セリウムHS(商品名)、平均粒径5μm、平均一次粒径8nm)を3g加え、その後、70℃で撹拌した。1時間後、沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化セリウムに金が固定化された固体触媒(Au/CeO2)を得た。得られた固体触媒の平均一次粒径は約8nmであり、金の固定化量は0.8質量%であり、担体上の金粒子の平均粒子径は4nmであった。
テトラクロロ金酸・四水和物22mgを蒸留水52mLに溶解させ、70℃に加温しながら、水酸化ナトリウム水溶液を滴下して、溶液のpHを7に調整した。これに酸化チタン(日本アエロジル(株)製、P-25(商品名)、平均一次粒径25nm)を1g加え、その後、70℃で撹拌した。1時間後、沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を100℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化チタンに金が固定化された固体触媒(Au/TiO2)を得た。得られた固体触媒の平均一次粒径は約25nmであり、金の固定化量は0.8質量%であり、担体上の金粒子の平均粒子径は3nmであった。
硝酸コバルト(II)・六水和物0.50gを蒸留水10mLに溶解させ、シリカ(富士シリシア化学(株)製、CARiACT Q-15(商品名)、平均一次粒径75-150μm)0.85gを加え、その後、テトラクロロ金酸・四水和物0.11gを加えた。室温で撹拌しながらアンモニア水を滴下して、溶液のpHを8.5に調整した。室温で1時間撹拌後、沈殿物を蒸留水で洗浄、濾過した。ろ物を120℃で20時間乾燥させた。乾燥後、400℃、空気中で5時間焼成を行うことで、シリカに金及びコバルトが固定化された固体触媒(Au/Co/SiO2)を得た。得られた固体触媒の平均一次粒径は約100μmであり、金の固定化量は4質量%であった。
テトラクロロ金酸・四水和物21mgを蒸留水51mLに溶解させ、水酸化ナトリウム水溶液を滴下して、溶液のpHを7.6に調整した。これに酸化コバルト-酸化セリウム(酸化コバルトと酸化セリウムの複合酸化物、平均一次粒径40nm)1gを加え、70℃で1時間撹拌し、その後、沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を70℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化コバルト-酸化セリウムに金が固定化された固体触媒(Au/Co3O4-CeO2)を得た。得られた固体触媒の平均一次粒径は約40nmであり、金の固定化量は0.7質量%であった。
テトラクロロ金酸・四水和物110mgを蒸留水180mLに溶解させ、尿素3.2g、二酸化マンガン(平均一次粒径40nm)1gの順に室温で加えた。その後、溶液を徐々に90℃まで加温し、90℃で18時間加熱撹拌を行った。沈殿物を蒸留水で洗浄、濾過した。得られたろ物を65℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、二酸化マンガンに金が固定化された固体触媒(Au/MnO2)を得た。得られた固体触媒の平均一次粒径は約40nmであり、金の固定化量は4質量%であり、担体上の金粒子の平均粒子径は5nmであった。
テトラクロロ金酸・四水和物22mgを蒸留水52mLに溶解させ、溶液を70℃に加温しながら、水酸化ナトリウム水溶液を滴下して、溶液のpHを7に調整した。調整後の溶液に酸化ジルコニウム(第一稀元素化学工業(株)製、RC-100(商品名)、平均一次粒径5nm)1gを加え、その後、70℃で撹拌した。1時間後、沈殿物をpHが一定になるまで蒸留水で洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化ジルコニウムに金が固定化された固体触媒(Au/ZrO2)を得た。得られた固体触媒の平均一次粒径は約5nmであり、金の固定化量は1質量%であり、担体上の金粒子の平均粒子径は4nmであった。
塩基性炭酸コバルト11gを300℃、空気中で4時間焼成を行うことで酸化コバルトを得た。
硝酸コバルト(II)・六水和物5.82gを蒸留水200mLに室温で溶解させた(水溶液7)。一方、これとは別に炭酸ナトリウム2.63gを蒸留水200mLに溶解させた(水溶液8)。次いで、上記水溶液7を上記水溶液8に一気に添加し、混合液を室温で3時間撹拌した。生成した沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を70℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化コバルトを得た。得られた酸化コバルトの平均一次粒径は約15nmであった。
テトラクロロ金酸・四水和物470mgを蒸留水66mLに溶解させ、室温で参考例1-10で調製した酸化コバルト2.0gを加え、水酸化ナトリウム水溶液を滴下して、pHを7に調整しながら室温で撹拌した。3時間後、沈殿物を蒸留水にて洗浄、濾過した。得られたろ物を65℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、析出沈殿法により酸化コバルトに金が固定化された固体触媒(Au/Co3O4)を得た。得られた固体触媒の金の固定化量は7質量%であった。
硝酸ランタン(III)・六水和物8.2g、及びテトラクロロ金酸・四水和物0.41gを蒸留水200mLに室温で溶解させた(水溶液9)。一方、これとは別に炭酸ナトリウム3.9gを蒸留水366mLに溶解させた(水溶液10)。次いで、上記水溶液9を上記水溶液10に一気に添加し、混合液を70℃で1.5時間撹拌した。生成した沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化ランタンに金が固定化された固体触媒(Au/La2O3)を得た。得られた固体触媒の金の固定化量は6質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素25gを蒸留水100mLに溶解させ、この溶液に酸化アルミニウム(住友化学(株)製、AKP-G015(商品名)、粒径100nm未満)1.0gを室温で加えた。その後、溶液を徐々に80℃まで加温し、80℃で8時間加熱撹拌を行った。50℃まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化アルミニウムに金が固定化された固体触媒(Au/Al2O3)を得た。得られた固体触媒の一次粒径は100nm未満であり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素25gを蒸留水100mLに溶解させ、この溶液に酸化ジルコニウム(第一稀元素化学工業(株)製、RC-100(商品名)、平均一次粒径5nm)1.0gを室温で加えた。その後、溶液を徐々に80℃まで加温し、80℃で8時間加熱撹拌を行った。50℃まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化ジルコニウムに金が固定化された固体触媒(Au/ZrO2)を得た。得られた固体触媒の平均一次粒径は約5nmであり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素2.5gを蒸留水100mLに溶解させ、この溶液に酸化ジルコニウム(第一稀元素化学工業(株)製、RC-100(商品名)、平均一次粒径5nm)1.0gを室温で加えた。その後、溶液を徐々に90℃まで加温し、90℃で4時間加熱撹拌を行った。室温まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を70℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化ジルコニウムに金が固定化された固体触媒(Au/ZrO2)を得た。得られた固体触媒の平均一次粒径は約5nmであり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素25gを蒸留水100mLに溶解させ、この溶液に酸化チタン(日本アエロジル(株)製、P-25(商品名)、平均一次粒子径25nm)1.0gを室温で加えた。その後、溶液を徐々に80℃まで加温し、80℃で8時間加熱撹拌を行った。50℃まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化チタンに金が固定化された固体触媒(Au/TiO2)を得た。得られた固体触媒の平均一次粒径は約25nmであり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素25gを蒸留水100mLに溶解させ、この溶液に酸化セリウム(第一稀元素化学工業(株)製、JRC-CEO-3(商品名)、平均一次粒子径11nm)1.0gを室温で加えた。その後、溶液を徐々に80℃まで加温し、80℃で8時間加熱撹拌を行った。50℃まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、酸化セリウムに金が固定化された固体触媒(Au/CeO2)を得た。得られた固体触媒の平均一次粒径は約11nmであり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物173mg及び尿素25gを蒸留水100mLに溶解させ、この溶液に酸化セリウム(第一稀元素化学工業(株)製、酸化セリウムHS(商品名)、平均一次粒子径8nm)1.0gを室温で加えた。その後、溶液を徐々に80℃まで加温し、80℃で8時間加熱撹拌を行った。50℃まで冷却した後、沈殿物を蒸留水で5回洗浄し、濾過した。得られたろ物を80℃で一晩乾燥させた。乾燥後、ろ物をU字型反応管に詰め、水素ガス18mL/分で4時間流通させながら200℃に加熱することで、酸化セリウムに金が固定化された固体触媒(Au/CeO2)を得た。得られた固体触媒の平均一次粒径は約8nmであり、金の固定化量は8質量%であった。
テトラクロロ金酸・四水和物220mgを蒸留水360mLに溶解させ、この溶液に尿素6.4g、及び三酸化二マンガン2g(アルドリッチ(株)製、平均一次粒子径40nm)を、この順で、室温で加えた。その後、溶液を徐々に90℃まで加温し、90℃で18時間加熱撹拌を行った。沈殿物を蒸留水で洗浄、濾過した。得られたろ物を65℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、三酸化二マンガンに金が固定化された固体触媒(Au/Mn2O3)を得た。得られた固体触媒の平均一次粒径は約40nmであり、金の固定化量は4質量%であり、担体上の金粒子の平均粒子径は9nmであった。
硫酸マンガン水和物3gを蒸留水50mLに溶解させ、この溶液を85℃に加温した。加温した溶液に、ペルオキソ二硫酸アンモニウム8.1gを蒸留水50mLに溶解させた溶液を徐々に加え、85℃で撹拌した。6時間後、得られた沈殿物を蒸留水で洗浄、濾過した。得られたろ物を65℃で乾燥させることにより二酸化マンガン(MnO2)を得た。得られた二酸化マンガンのX線回折(XRD)パターンを図3に示す。
テトラクロロ金酸・四水和物220mgを蒸留水360mLに溶解させ、尿素6.4g、参考例1-21で調製した二酸化マンガン2gの順に室温で加えた。その後、反応液を徐々に90℃まで加温し、90℃で18時間加熱撹拌を行った。沈殿物を蒸留水で洗浄、濾過した。得られたろ物を65℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行うことで、二酸化マンガンに金が固定化された固体触媒(Au/MnO2)を得た。得られた固体触媒の金の固定化量は5質量%であった。
ヘキサニトラトセリウム(IV)酸アンモニウム12g、硝酸ランタン6水和物1.1g、及び尿素24gを蒸留水200mLに溶解させ、この溶液を還流下で撹拌した。8時間後、沈殿物を蒸留水にて洗浄、濾過した。ろ物を80℃で乾燥させた。乾燥後、400℃、空気中で7時間焼成することによりランタンがドープされた酸化セリウム(Ce(La)O2)を得た。得られたランタンがドープされた酸化セリウムの平均一次粒径は4nmであった。
ヘキサニトラトセリウム(IV)酸アンモニウム12g、硝酸ジルコニウム0.7g、及び尿素24gを蒸留水200mLに溶解させ、この溶液を還流下で撹拌した。8時間後、沈殿物を蒸留水にて洗浄、濾過した。ろ物を80℃で乾燥させた。乾燥後、400℃、空気中で7時間焼成することによりジルコニウムがドープされた酸化セリウム(Ce(Zr)O2)を得た。得られたジルコニウムがドープされた酸化セリウムの平均一次粒径は4nmであった。
テトラクロロ金酸・四水和物43mgを蒸留水100mLに溶解させ、70℃に加温しながら、水酸化ナトリウム水溶液を滴下して、溶液のpHを7-8に調整した。これに参考例1-23で調製したCe(La)O2を1g加え、その後、70℃で撹拌した。1時間後、沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行った。さらに300℃、水素下で還元することで、ランタンがドープされた酸化セリウムに金が固定化された固体触媒(Au/Ce(La)O2)を得た。得られた固体触媒の平均一次粒径は4nmであり、金の固定化量は1質量%であり、担体上の金粒子の平均粒子径は3nmであった。
テトラクロロ金酸・四水和物43mgを蒸留水100mLに溶解させ、70℃に加温しながら、水酸化ナトリウム水溶液を滴下して、溶液のpHを7-8に調整した。これに参考例1-23で調製したCe(Zr)O2を1g加え、その後、70℃で撹拌した。1時間後、沈殿物をpHが一定になるまで蒸留水にて洗浄、濾過した。ろ物を80℃で一晩乾燥させた。乾燥後、300℃、空気中で4時間焼成を行った。さらに300℃、水素下で還元することで、ジルコニウムがドープされた酸化セリウムに金が固定化された固体触媒(「Au/Ce(Zr)O2」を得た。得られた固体触媒の平均一次粒径は4nmであり、金の固定化量は1質量%であり、担体上の金粒子の平均粒子径は3nmであった。
内容積25mLの3つ口フラスコにo-フタル酸ジメチル3.5g(18mmol)、実施例1-1で調製したAu/Co3O4 1.9g(o-フタル酸ジメチルに対し6mol%)、及び酢酸7mLを導入した。上記反応容器を、予め125℃に設定しておいたオイルバスに浸けて、72時間反応させた後、分析した結果、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率11%で生成していた。さらに24時間反応させ、収率が変わらず11%であったことから、反応が停止していることを確認した。沈殿物を濾過し、ろ物をアセトンで洗浄した。洗浄したろ物を減圧下100℃で乾燥することにより、酸化コバルトに金が固定化された固体触媒(Au/Co3O4)を得た。この固体を300℃、空気中で4時間焼成を行うことで、焼成処理された固体触媒(Au/Co3O4)を得た。得られた固体触媒の粒径は5~20nmであり、担体上の金粒子の平均粒子径は8nmであった。
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、o-フタル酸ジメチル0.27g(1.4mmol)、実施例1-1で調製したAu/Co3O4 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸2.7mLを導入した。その後、反応系内の圧力が2.5MPaとなるように空気を圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを水冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率20%で生成していた(s/a比=10)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、o-フタル酸ジメチル0.23g(1.2mmol)、実施例1-1で調製したAu/Co3O4 0.15g(o-フタル酸ジメチルに対し7mol%)、及び酢酸0.8mLを導入した。反応系内を窒素ガスに置換した後、反応系内の圧力が1.0MPaとなるように窒素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを水冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率21%で生成していた(s/a比=7)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、o-フタル酸ジメチル2.78g(14.3mmol)、及び実施例1-1で調製したAu/Co3O4 26mg(o-フタル酸ジメチルに対し0.1mol%)を導入した。反応系内の圧力が2.5MPaとなるように空気を圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、40時間反応させた。さらに、オイルバスを200℃に加温し、20時間反応させた。反応終了後、オートクレーブを水冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=2)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 74mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸とジオキサンの混合液(酢酸:ジオキサン=1:1(体積比))0.4mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率25%で生成していた(s/a比=13)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 74mg(o-フタル酸ジメチルに対し4mol%)、及び酪酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率11%で生成していた(s/a比=6)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 74mg(o-フタル酸ジメチルに対し4mol%)、及びイソ吉草酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率2%で生成していた(s/a比=100)。
内容積10mLガラス製シュレンク管に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 74mg(o-フタル酸ジメチルに対し4mol%)、及びプロピオン酸0.4mLを導入した。反応系内を常圧で窒素ガスに置換した後、上記シュレンク管を、予め150℃に設定しておいたオイルバスに浸けて、34時間反応させた。反応終了後、シュレンク管を空冷してシュレンク管内のガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率5%で生成していた(s/a比=4)。
内容積10mLガラス製シュレンク管に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 73mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.4mLを導入した。反応系内を常圧で窒素ガスに置換した後、上記シュレンク管を、予め125℃に設定しておいたオイルバスに浸けて、67時間反応させた。反応終了後、シュレンク管を空冷してシュレンク管内のガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率22%で生成していた(s/a比=13)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-2で調製したAu/NiO 100mg(o-フタル酸ジメチルに対し6mol%)、及び酢酸0.4mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率11%で生成していた(s/a比=3)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-3で調製したAu/Fe2O3 70mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.4mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率6%で生成していた(s/a比=6)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-4で調製したAu/CeO2 0.15g(o-フタル酸ジメチルに対し0.8mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率17%で生成していた(s/a比=4)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-5で調製したAu/TiO2 0.15g(o-フタル酸ジメチルに対し0.8mol%)、及び酢酸0.4mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率2%で生成していた(s/a比=2)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-6で調製したAu/Co/SiO2 0.20g(o-フタル酸ジメチルに対し5mol%)、及び酢酸0.4mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率13%で生成していた(s/a比=3)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-7で調製したAu/Co3O4-CeO2 0.40g(o-フタル酸ジメチルに対し2mol%)、及び酢酸0.7mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=100)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-9で調製したAu/ZrO2 0.15g(o-フタル酸ジメチルに対し0.8mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率21%で生成していた(s/a比=7)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-7で調製したAu/Co3O4-CeO2 0.15g(o-フタル酸ジメチルに対し0.75mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率27%で生成していた(s/a比=14)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-12で析出沈殿法を用いて調製したAu/Co3O4 70mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.4mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、24時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率12%で生成していた(s/a比=10)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-13で調製したAu/La2O3 0.13g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率3%で生成していた(s/a比=3)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-14で調製したAu/Al2O3 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率23%で生成していた(s/a比=5)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-15で調製したAu/ZrO2 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.85MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率45%で生成していた(s/a比=8)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-16で調製したAu/ZrO2 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.85MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め140℃に設定しておいたオイルバスに浸けて、48時間反応させた。反応終了後、オートクレーブを空冷して、オートクレーブからガスを開放した。得られた反応液ガスクロマトグラフィーによりを分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率58%で生成していた(s/a比=15)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-17で調製したAu/TiO2 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、72時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率31%で生成していた(s/a比=4)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-18で調製したAu/CeO2 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率28%で生成していた(s/a比=7)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、o-フタル酸ジメチル0.20g(1mmol)、実施例1-19で調製したAu/CeO2 0.10g(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、オートクレーブからガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率25%で生成していた(s/a比=7)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-20で析出沈殿法を用いて調製したAu/Mn2O3 0.21g(o-フタル酸ジメチルに対し6mol%)、及び酢酸0.4mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、反応させた。反応開始140時間後と207時間後にAu/Mn2O3 0.21g(o-フタル酸ジメチルに対し6mol%)をそれぞれ加え、反応開始から合計で279時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率58%で生成していた(s/a比=20)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-22で析出沈殿法を用いて調製したAu/MnO2 71mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.4mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、48時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率17%で生成していた(s/a比=28)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.10g(0.5mmol)、実施例1-27で焼成処理を行ったAu/Co3O4 36mg(o-フタル酸ジメチルに対し4mol%)、及び酢酸0.2mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、41時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率7%で生成していた(s/a比=15)。
内容積2mLのガラス製反応容器に、o-フタル酸ジメチル0.40g(2.1mmol)、及び実施例1-12で析出沈殿法を用いて調製したAu/Co3O4 0.141g(o-フタル酸ジメチルに対し4mol%)を導入した。空気下常圧、上記反応容器を予め150℃に設定しておいたオイルバスに浸けて、24時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率9%で生成していた(s/a比=2)。
内容積2mLのガラス製反応容器に、o-フタル酸ジメチル0.41g(2.1mmol)、及び実施例1-1で共沈法を用いて調製したAu/Co3O4 0.142g(o-フタル酸ジメチルに対し4mol%)を導入した。空気下常圧、上記反応容器を予め200℃に設定しておいたオイルバスに浸けて、24時間反応させた。反応終了後、空冷して得られた反応液ガスクロマトグラフィーによりを分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=2)。
内容積2mLのガラス製反応容器に、o-フタル酸ジメチル0.40g(2.1mmol)、及び実施例1-12で析出沈殿法を用いて調製したAu/Co3O4 0.144g(o-フタル酸ジメチルに対し4mol%)を導入した。空気下常圧、上記反応容器を予め200℃に設定しておいたオイルバスに浸けて、24時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率8%で生成していた(s/a比=2)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.21g(1.1mmol)、実施例1-25で調製したAu/Ce(La)O2 84mg(o-フタル酸ジメチルに対し0.4mol%)、及び酢酸0.4mLを導入した。空気下常圧、上記反応容器を予め125℃に設定しておいたアルミブロックに接触させ、100時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率9%で生成していた(s/a比=15)。
内容積30mLのガラス製反応容器に、o-フタル酸ジメチル0.21g(1.1mmol)、実施例1-26で調製したAu/Ce(Zr)O2 84mg(o-フタル酸ジメチルに対し0.4mol%)、及び酢酸0.4mLを導入した。空気下常圧、上記反応容器を予め125℃に設定しておいたアルミブロックに接触させ、48時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=9)。
ガラス内挿管が付属していないSUS製オートクレーブ(内容積10mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-5で調製したAu/TiO2 85mg(o-フタル酸ジメチルに対し金0.4mol%)、及び1H,1H-トリデカフルオロ-1-ヘプタノール0.2mLを導入した。反応系内の圧力が2.5MPaとなるように空気を圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、24時間反応させた。反応終了後、オートクレーブを空冷してガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=1)。
ガラス内挿管が付属していないSUS製オートクレーブ(内容積10mL)に、o-フタル酸ジメチル0.20g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(o-フタル酸ジメチルに対し金4mol%)、及び1H,1H-トリデカフルオロ-1-ヘプタノール0.3mLを導入した。反応系内の圧力が2.5MPaとなるように空気を圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、16時間反応させた。反応終了後、オートクレーブを空冷してガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステル(s-DM)が収率1%で生成していた(s/a比=1)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、o-キシレン0.11g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(o-キシレンに対し4mol%)、及び酢酸0.4mLを導入した。反応系内を窒素ガスに置換した後、反応系内の圧力が0.5MPaとなるように窒素ガスを圧入した。次いで、上記オートクレーブを、予め125℃に設定しておいたオイルバスに浸けて、24時間反応させた。反応終了後、オートクレーブを水冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-テトラメチルビフェニルが収率3.2%で生成していた。
撹拌装置、加熱還流装置を備えた内容積5mL反応容器に、o-キシレン0.11g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(o-キシレンに対し4mol%)、及び酢酸0.4mLを導入した。反応系内を窒素ガスに置換した後、窒素バルーンを取り付けた状態で、加熱部を予め125℃に設定して51時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-テトラメチルビフェニルが収率7.5%で生成していた。
撹拌装置、加熱還流装置を備えた内容積5mL反応容器に、安息香酸メチル0.14g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(安息香酸メチルに対し4mol%)、及び酢酸0.4mLを導入した。反応系内を窒素ガスに置換した後、窒素バルーンを取り付けた状態で、加熱部を予め125℃に設定して51時間反応させた。反応終了後、空冷して得られた反応液をガスクロマトグラフィーにより分析したところ、4,4’-ビフェニルジカルボン酸ジメチルが収率3.3%で生成していた。
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、トルエン0.09g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(トルエンに対し4mol%)、及び酢酸0.4mLを導入した。反応系内を窒素ガスに置換した後、反応系内の圧力が0.5MPaとなるように窒素ガスを圧入した。次いで、上記オートクレーブを、予め125℃に設定しておいたオイルバスに浸けて、25時間反応させた。反応終了後、オートクレーブを水冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析した。ガスクロマトグラフィーのチャートを図1に示す。ガスクロマトグラフィーのチャート(図1)では、トルエンの二量体(ジメチルビフェニル)に相当するピークが6種観測され、そのうちの保持時間15.9分の位置に観測されるピークは、4,4’-ジメチルビフェニルのピークであった。
撹拌装置、加熱還流装置を備えた内容積5mL反応容器に、安息香酸0.12g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(安息香酸に対し4mol%)、及び酢酸0.4mLを導入した。反応系内を窒素ガスに置換した後、窒素バルーンを取り付けた状態で、加熱部を予め125℃に設定し、51時間反応させた。反応終了後、空冷して得られた反応液を高速液体クロマトグラフィー(HPLC)により分析した。HPLCのチャートを図2に示す。保持時間8.5分、8、7分、8.9分のピークについてHPLC/MSにより分析したところ、安息香酸の二量体に相当する分子量のピークで有る事が確認された。
装置:島津製作所製 LC-20AB
カラム:Waters Atlantis dC18 5μmΦ4.6×150mm
溶離液:A:0.1%HCOOH水溶液、B:CH3CN
タイムプログラム:0.01分:A/B=70/30、20.00分:A/B=5/95、25.00分:A/B=5/95、25.01分:A/B=70/30、40.00分:A/B=70/30
流量:1mL/分
検出器:254nm
ガラス内挿管が付属したSUS製オートクレーブ(内容積50mL)に、キシレン(o-,m-,p-体の混合物)0.52g(4.9mmol)、及び実施例1-8で調製したAu/MnO2 0.15g(キシレンに対し0.8mol%)を導入した。反応系内の圧力が0.5MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを予め100℃に設定しておいたオイルバスに浸けて、19時間反応させた。反応終了後、オートクレーブを空冷してガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーによりガスクロマトグラフィーにより分析したところ、キシレンの二量体(テトラメチルビフェニル)の生成が確認できた。
内容積13mLのパイレックス(登録商標)ガラス製バイアル瓶に、o-キシレン0.11g(1mmol)、実施例1-1で調製したAu/Co3O4 74mg(o-キシレンに対し4mol%)、及び酢酸0.5mLを導入した。空気下常圧で、上記反応容器を予め130℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-テトラメチルビフェニルが収率13%で生成していた(s/a比=7)。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、トリフルオロメチルベンゼン0.15g(1mmol)、実施例1-1で調製したAu/Co3O4 74mg(トリフルオロメチルベンゼンに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、4,4’-ビストリフルオロメチルビフェニルが収率4%で生成していた。
内容積13mLのパイレックス(登録商標)ガラス製バイアル瓶に、p-ジメトキシベンゼン0.14g(1mmol)、実施例1-1で調製したAu/Co3O4 74mg(p-ジメトキシベンゼンに対し4mol%)、及び酢酸0.5mLを導入した。空気下常圧で、上記反応容器を予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、2,2’,5,5’-テトラメトキシビフェニルが収率21%で生成していた。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、tert-ブチルベンゼン0.13g(1mmol)、実施例1-1で調製したAu/Co3O4 75mg(tert-ブチルベンゼンに対し4mol%)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、66時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、4,4’-ジ-tert-ブチルビフェニル、4,3’-ジ-tert-ブチルビフェニル及び3,3’-ジ-tert-ブチルビフェニルの混合物が合計62%の収率で生成していた。
内容積30mLのガラス製反応容器に、o-ジメトキシベンゼン0.14g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(o-ジメトキシベンゼンに対し4mol%)、及び酢酸0.4mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、15時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-テトラメトキシビフェニルが収率19%で生成していた。
内容積30mLのガラス製反応容器に、2,3,6-トリメチルフェノール0.14g(1.0mmol)、実施例1-1で調製したAu/Co3O4 72mg(2,3,6-トリメチルフェノールに対し4mol%)、及び酢酸0.4mLを導入した。空気下常圧で、上記反応容器を、予め125℃に設定しておいたアルミブロックに接触させ、22時間反応させた。反応終了後、反応溶液を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、2,2’,3,3’,5,5’-ヘキサメチル-[ビフェニル]-4,4’-ジオールが収率46%で生成していた。
内容積30mLのガラス製シュレンク管に、o-フタル酸ジメチル0.21g(1.1mmol)、テトラクロロ金酸・四水和物24mg(o-フタル酸ジメチルに対し6mol%)、及び酢酸0.4mLを導入した。上記シュレンク管を、予め125℃に設定しておいたオイルバスに浸けて、空気下常圧にて20時間反応させた。反応終了後、シュレンク管を空冷した。得られた反応液をガスクロマトグラフィーにより分析したところ、3,3’,4,4’-ビフェニルテトラカルボン酸テトラメチルエステルの生成は全く認められなかった。
内容積10mLのガラス製反応容器に、実施例1-1で調製したAu/Co3O4 75mg、及び酢酸0.4mLを導入した。窒素ガス雰囲気下常圧で、上記反応容器を、予め125℃に設定しておいたオイルバスに浸けて、1時間加熱撹拌を行った。加熱撹拌終了直後に、溶液を熱時濾過し、125℃に加熱しておいた酢酸3mLでろ物を洗浄した。得られたろ液中をICP-AESを用いて分析したところ、Auは検出されなかった。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、tert-ブチルベンゼン0.13g(1mmol)、参考例1-11で調製したCo3O4 66mg(0.27mmol)、及び酢酸0.5mLを導入した。反応系内の圧力が1.6MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、多価置換ビフェニル化合物の収率は0%であった。
ガラス内挿管が付属したSUS製オートクレーブ(内容積30mL)に、p-ジメトキシベンゼン0.14g(1mmol)、参考例1-11で調製したCo3O4 66mg(0.27mmol)、及び酢酸0.5mLを導入した。反応系内の圧力が0.2MPaとなるように酸素ガスを圧入した。次いで、上記オートクレーブを、予め150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、オートクレーブを空冷して、ガラス内挿管からガスを開放した。得られた反応液をガスクロマトグラフィーにより分析したところ、多価置換ビフェニル化合物の収率は0%であった。
内容積13mLのパイレックス(登録商標)ガラス製バイアル瓶に、o-キシレン0.11g(1mmol)、参考例1-11で調製したCo3O4 66mg(0.27mmol)、及び酢酸0.5mLを導入した。空気下常圧で、前述の反応容器を150℃に設定しておいたオイルバスに浸けて、18時間反応させた。反応終了後、反応溶液を空冷して、得られた反応液をガスクロマトグラフィーにより分析したところ、多価置換ビフェニル化合物の収率は0%であった。
内容積100mLのチタン製オートクレーブに、実施例2-15で合成した3,3’,4,4’-テトラメチルビフェニル2.10g(10mmol)、酢酸コバルト四水和物12.4mg(0.05mmol)、酢酸マンガン四水和物12.2mg(0.05mmol)、N-ヒドロキシフタルイミド(以下、「NHPI」と称する)163mg(1mmol)、及び酢酸15mLを導入し、空気雰囲気(内圧3MPa)にて、150℃で反応を行った。反応開始1時間後、オートクレーブを室温まで冷却し、オートクレーブ内のガスを開放した。オートクレーブ内にさらにNHPI 163mgを添加した後、150℃で反応を再開した。1時間後に再びこの一連の操作(冷却-ガス解放-添加-反応再開)を繰り返し、合計3時間反応を行った。反応終了後、オートクレーブを室温まで冷却して、オートクレーブ内のガスを開放した。得られた反応液から溶媒を留去し、そこへ酢酸エチルと水を加えて分液した後、酢酸エチル層を水で洗浄して金属化合物を除去し、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物を得た。
Claims (16)
- 担体に金が固定化された固体触媒の存在下で、下記一般式(1)で表される置換ベンゼン化合物をカップリングさせる工程を備える、下記一般式(2)で表される多価置換ビフェニル化合物の製造方法。
- 前記一般式(1)で表される置換ベンゼン化合物が下記一般式(1)’で表される置換ベンゼン化合物であり、前記一般式(2)で表される多価置換ビフェニル化合物が下記一般式(2)’で表される化合物である、請求項1に記載の多価置換ビフェニル化合物の製造方法。
- 前記一般式(1)及び(2)中の前記Rがアルキル基、カルボキシル基又はアルコキシカルボニル基である、請求項1に記載の多価置換ビフェニル化合物の製造方法。
- 前記一般式(1)’及び(2)’中の前記Rがアルキル基、カルボキシル基又はアルコキシカルボニル基である、請求項2に記載の多価置換ビフェニル化合物の製造方法。
- 前記担体が金属酸化物である、請求項1~5のいずれか一項に記載の多価置換ビフェニル化合物の製造方法。
- 前記金属酸化物が、コバルト(Co)、マンガン(Mn)、鉄(Fe)、セリウム(Ce)、ジルコニウム(Zr)、ニッケル(Ni)、チタン(Ti)、ランタン(La)、ケイ素(Si)及びアルミニウム(Al)からなる群より選ばれる少なくとも一種の金属の酸化物である、請求項6に記載の多価置換ビフェニル化合物の製造方法。
- 前記金属酸化物がマンガン(Mn)、コバルト(Co)及びジルコニウム(Zr)からなる群より選ばれる少なくとも一種の金属の酸化物である、請求項6に記載の多価置換ビフェニル化合物の製造方法。
- 前記担体に0.5~10nmの平均粒子径を有する金粒子が固定化されている、請求項1~8のいずれか一項に記載の多価置換ビフェニル化合物の製造方法。
- 前記工程において、前記一般式(1)で表される置換ベンゼン化合物をさらに溶媒の存在下でカップリングさせ、前記溶媒が有機カルボン酸である、請求項1~9のいずれか一項に記載の多価置換ビフェニル化合物の製造方法。
- 前記有機カルボン酸が酢酸である、請求項10に記載の多価置換ビフェニル化合物の製造方法。
- 前記工程において、前記一般式(1)で表される置換ベンゼン化合物を酸素を含むガス中でカップリングさせる、請求項1~11のいずれか一項に記載の多価置換ビフェニル化合物の製造方法。
- 前記担体が金属酸化物である、請求項13に記載の多価置換ビフェニル化合物製造用固体触媒。
- 前記金属酸化物がマンガン(Mn)、コバルト(Co)及びジルコニウム(Zr)
からなる群より選ばれる少なくとも一種の金属の酸化物である、請求項14に記載の多価置換ビフェニル化合物製造用固体触媒。
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JP2019172628A (ja) * | 2018-03-29 | 2019-10-10 | 国立大学法人九州大学 | アリル化合物の異性化方法 |
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US20150274689A1 (en) | 2015-10-01 |
CN104703949A (zh) | 2015-06-10 |
KR20150064171A (ko) | 2015-06-10 |
CN104703949B (zh) | 2017-04-05 |
KR102121635B1 (ko) | 2020-06-10 |
JP6241826B2 (ja) | 2017-12-06 |
US9469621B2 (en) | 2016-10-18 |
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